An efficient ionic liquid with both Brønsted acidic and Lewis basic sites, namely 1,4-dimethyl-1- (4-sulphobutyl)piperazinium hydrogen sulphate (IL1), was synthesised and characterised. IL1 is a “green”, homogeneous and reusable catalyst for: i) the synthesis of pyranopyrazoles (Va–Vj) and benzopyrans (VIa–VIj and VIIa–VIIf) at ambient temperature under solvent-free conditions and ii) the synthesis of amino-2-chromenes (VIIIa–VIIIi and IXa–IXi) and dihyropyrano[c]chromenes (Xa– Xi) at 80◦C under solvent-free conditions. The reactions were rapid with excellent product yields. In addition, the double Brønsted acid, 1,4-dimethyl-1,4-bis(4-sulphobutyl)piperazinium hydrogen sulphate (IL2), was prepared to evaluate the cooperation efficiency of their Brønsted acidic and Lewis basic sites as compared with the double Brønsted acidic sites in IL1.